Adsorption of Ethoxylated Sulfonate and Nonionic Homologs on Coal

M. S. C E L I K 1
K. F. University of Petroleum & Minerals, KFUPM Box 785, Dhahran, 31261 Saudi Arabia
Received March 17, 1988; accepted July 6, 1988

The adsorption of ethoxylated sulfonates and nonionics of the same ethoxylation number on a low-
ash coal has been studied. The surfactant adsorption has been investigatedas a function of concentration,
pH, temperature, and ionic strength for three homologs. The zeta potential of the coal particles and the
surface tension of the supernatants have been concurrently determined to elucidate the orientation of
surfactant molecules on the coal surface as well as the mechanism of adsorption. The adsorption data
are utilized to calculatethermodynamic parameters such as the free energyof adsorption and the isoteric
heats of adsorption. 1989 Academic Press, Inc.

INTRODUCTION mechanism of adsorption as well as the m o d e

The adsorption properties of nonionic sur-
factants at the solid-liquid interface are im-
portant in a n u m b e r o f industrial processes
such as flotation, flocculation, dispersion,
emulsification, and dewatering (1). Adsorption
studies with nonionic surfactants on carbon
have been extensively dealt with in the liter-
ature (2). There is also an upsurge of interest
in the use of surfactants in coal technology
( 3 - 5 ) . However, fundamental aspects of the
underlying p h e n o m e n a are still not well un-
derstood due to the complexity of the coal
substance which incorporates a variety of
mineral constituents. Some recent studies have
utilized demineralized coals to investigate the
effect of mineral matter on some properties of
coal ( 6 - 9 ) . There is, however, a need to use
natural coals with low ash content in order to
better understand the way nonionic surfac-
tants interact with coal.
In this study, the adsorption, electrokinetic,
and surface tension properties of two series of
nonionic surfactant and ethoxylated sulfonate
homologs on a low-ash coal have been ex-
amined. The data are analyzed to identify the
l Present address: Department of Mining and Minerals
Engineering, Virginia Polytechnic Institute and State
University, Blacksburg,VA 24061.
and configuration of the adsorbed surfactant
molecules at the coal surface.
EXPERIMENTAL
Materials
Buehler seam coal (0.13% ash by weight)
in. in size from New Zealand was passed
through a roll crusher to obtain a + 100-mesh
fraction. The sub-100-mesh fraction was dis-
carded to avoid any iron contamination. The
+100-mesh fraction was further ground in a
coffee grinder for 10 min. This coal sample
was sealed in a plastic zipper bag and was kept
in a freezer for subsequent use in adsorption
tests. The specific surface area of this coal by
BET technique using nitrogen adsorbate was
found to be 26.9 m2/g. Earlier surface area
measurements (9) on the same coal by means
of air permeametry and BET technique re-
vealed this particular coal to have insignificant
microporosity.
The tributylphenol polyglycolethers
(C3xq~Ey) a n d e t h o x y l a t e d sulfonates
(Cax ~bEyS ) are products of Hoechst Chemical
Co. For the sake of convenience these surfac-
tants will be further abbreviated as E r and EyS,
respectively. The symbols x, , y, and S re-
spectively denote the n u m b e r of CH2 groups
in the alkyl chain, the benzene ring, the n u m -
ber of EO units in the polymer, and the anionic

428
0021-9797/89 $3.00
Copyright 1989 by Academic Press, Inc.
All rights of reproduction in any form reserved. Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
 SURFACTANT ADSORPTION ON COAL 429

TABLE I

Thermodynamic Data for Coal/Surfactant System

Surfactant Surfaceexcess(F) CMC Area per molecule AG~t~ AG~i~ AH~t~

designation (mole/m2) (kmole/m3) (A2) (kcal/mole) (kcal/mole) (kcal/mole)

a
E13 2.01 X 10-7 1.0 X 10-4 719 -6.72 -5.40
Ej5 1.56 X 10-7 1.2 10-4 1278 -6.85 -5.22 -0.90
El8 1.00 X 10-7 1.6 X 10-4 1941 --7.09 --5.11

EloS 2.31 X 10-7 1.1 X 10-4 826 --6.66 --5.46

E15S 1.30 X 10-7 1.5 X 10-4 1065 --6.95 --5.35 -0.79
EIsS 8.56 X 10-8 1.8 X 10-4 1661 -7.17 -5.18

C4H 9 C4H 9

C 4 H 9 - ~ O - - (CH2. CH2. O)y H C 4 H 9 ~ O - - (CH 2"CH 2" O)y SO3Na+

C4H9 C4H 9

sulfonate group. Some of the properties of
these surfactants are listed in Table I. Sodium
dodecylbenzenesulfonate (NaDDBS) of 85%
purity was purchased from Pfaltz & Bauer. All
the solutions were prepared using distilled and
deionized water.
Methods
The adsorption experiments were con-
ducted in 35-ml sealed screw-cap Teflon vials.
Thirty milliliters of a surfactant solution of
known concentration having 2 10 -3 kmole/
m 3 NaC1 was introduced into a vial containing
0.3 g of coal sample. The samples were con-
ditioned in a constant temperature shaking
water bath for 6 h, centrifuged, and then kept
undisturbed at the same temperature for an
additional 6 h. This procedure was necessary
to eliminate the perturbations caused during
centrifugation at a lower temperature. The
equilibrium concentration ofsurfactant in the
supernatant was determined spectrophoto-
metrically from the optical density at 276 nm.
The amount adsorbed was calculated from the
difference between the initial and final con-
centrations.
The zeta potential measurements were per-
formed by a Zeta Meter 3.0 equipped with a
microprocessor unit. The measurements were
made on particles over a micrometer in size
in order to keep the ratio of particle radius of
curvature to electrical double-layer thickness
large. The samples were taken from the actual
supernatants following the adsorption tests.
About 22 ml of a clear supernatant was re-
moved from the adsorption test vial and in-
troduced into a Pyrex electrophoresis cell. An
appropriate amount of coal particles was pi-
petted out of the coal bed and placed in the
cell. This procedure assured elimination of
very fine coal particles which produced a black
color and worsened the visibility of coal par-
ticles.
The critical micelle concentration (CMC)
of all surfactants was determined by means of
the surface tension technique. A Kruss digital
tensiometer with the ring method was utilized.
The CMC was determined in the presence of
2 X 10 -3 k m o l e / m 3 NaC1 for both the pure
surfactants and the actual supernatants fop
lowing the adsorption tests. All surface tension
measurements were carried out at 25C.
RESULTS AND DISCUSSION
CMC Measurements
The CMC values for both Ey and EyS ho-
mologs are plotted in Fig. 1 as a function of
Journal of ColloM and Interface Science, Vol. 129,No. 2, May 1989
430
3xlff ~
2xiC A
t~E
ixio-4
6Xlff 5
FIG. l. CMCdependenceofnonionicsand ethoxylatedsulfonatesvs EOnumber.
the ethoxylation (EO) number. It is evident
that the CMC values for the two series yielded
straight lines on a semilog plot with slightly
different slopes. The ethoxylated sulfonates
produced higher CMCs than the nonionics of
the same EO number; this behavior is consis-
tent with the respective surface activity of each
class of surfactant. The presence of the sul-
fonate group in the ethoxylated sulfonate op-
poses micellization and in turn results in
higher CMCs~ The CMC values are generally
in agreement with the reported literature val-
ues for similar surfactants (10-11). It should
be noted that the CMC values obtained from
the actual supernatants were slightly higher for
all surfactants tested. Similarly, the surface
tension measurements on the actual super-
natants gave higher values by up to 1 m N / m
than those on pure solutions, probably due to
release of ions and organic humic acid-like
substances from the coal matrix (12).
Zeta Potential Measurements
The results of zeta potential measurements
vs pH for the two series of surfactants are pre-
sented in Figs. 2 and 3. In the absence of any
surfactant the coal exhibited an isoelectric
point (iep) of approximately 5, which falls
within the iep values reported in the literature
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
M.S. CELIK
2XlO-3kmol/m3 NaCI
T- 25 C
o EyS
Ey
I, I I I I
10 12 14 16 18
EO NUMBER ( y )
(8, 13, 14). However, in the presence of 4
X 10 -4 kmole/m 3 of nonionic surfactant
comprising different EO numbers, an inter-
esting observation was made in that the iep of
all surfactants shifted about 2.2 units toward
the alkaline pH. A similar observation was also
made previously with polyoxyethylene non-
ylphenol homologs (9).
This observation can be ascribed to a shift
either of iep or of the shear plane (15). Ad-
sorption of nonionic surfactants on coal at low
coverages is believed to occur through the hy-
drocarbon part of the molecule lying flat on
the hydrophobic surface (2). If the adsorption
energy of the surfactant is greater than that of
the water molecules, displacement of some of
the water dipoles will lead to a change in the
Stern potential due to decreased dipolar in-
teractions. Mechanical displacement of the
shear plane, on the other hand, can result due
to adsorbed bulky surfactant molecules being
projected some distance beyond the original
shear plane (15).
In the present system, the nonionic surfac-
tant, irrespective of its EO number, produces
the same shift of the shear plane as illustrated
in Fig. 2. This can be explained by the fact
that the water molecules are displaced by the
hydrocarbon chain alone and the contribution
of the EO chain is minimal. Since the nonionic
 SURFACTANT ADSORPTION ON COAL 431

+60

0 NO SURFACTANT
o El3
+40 E15
El8

+20
>
E

I
12
o pH

-20
COAL/4XIO-4 k~l/m 3 EY ~ a

2X]O-3 kmol/m3 NaCI X

-40
T= 25C 0"~

-60

FIG, 2. Variation of zeta potential of coal with pH in the absence and presence of surfactant.

chain itself does not contribute to any free
changes in the electrical double layer, the ad-
sorbed molecules reduce the surface charge
only by covering the adsorbed sites on both
sides of the iep. Consequently, the reduced zeta
potential vs pH curves exhibited symmetry
with respect to the iep. The results presented
above reveal that displacement of the water
molecules by the alkyl chain followed by a de-
crease in dipolar interactions is responsible for
the observed shift in Stern potential. Mechan-
ical displacement is unlikely as it would induce
different shifts with increased EO chain length.
Figure 3 presents the zeta potential vs pH
data obtained with ethoxylated sulfonates of
varying EO number. Included in the data is

-50

-40
0 0 o
'0 ,0 0 v
Lt, & W
& La
, -30 COAL/4XlO-4kmol/m3 E S
Y
2X10-3krm)l/m3 NaCI
T= 25 C
-20

0 E18S
oE S
15
-10 t, EIoS
NaDDBS

| i t I i i

2 4 6 8 10 12 14
pH

FIG. 3. Zeta potential of coal in the presence of ethoxylated sulfonates and NaDDBS.
Journal of Colloid and Interface Science, Vol. 129, No, 2, May 1989
432
NaDDBS with a linear hydrocarbon chain.
Unlike nonionics, ethoxylated sulfonates
demonstrated constant negative zeta potentials
in the entire pH range tested. Slight increases
in the negative zeta potentials with increases
in the EO number seem to be contrary to the
data on magnitude of adsorption (see Fig. 5 ).
This anomaly can be ascribed to the increasing
equilibrium pH values found upon increasing
the EO number. For instance, the equilibrium
pH values for the nonionic surfactants were
approximately 7.5, 8.0, and 9.0, respectively.
Although increasing pH in the range 7.5 to 9.0
does not affect the adsorption capacity of the
surfactant, it concurrently increases the zeta
potentials. Interestingly, the ethoxylated sul-
fonates did not exhibit an iep shift similar to
that observed in the case of nonionics of the
same structure and EO number. This finding
clearly reveals the role of charged sulfonate
groups in controlling the double-layer prop-
erties. The zeta potential results further dem-
onstrate that the hydrocarbon part of the sur-
factant molecule has equal affinity to the coal
surface both below and above the iep.
2.4
EIoS
2.0 E13
c,J
"~ 1.6
q5
r.. E15S
o
vx 1.2
N E18S
~: 0.4
i I
2 4
FIG. 4. Adsorption of various surfactants on coal as a function of pH.
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
M.S. CELIK
Similarly, NaDDBS, which is devoid of EO
units, showed that coal is equally receptive to
nonpolar chains irrespective of its charge.
NaDDBS produced higher negative zeta po-
tential values than the ethoxylated sulfonates.
Processes governed by physical adsorption
usually involve electrostatic interactions. For
instance, adsorption of amine on oxidized coal
is reported to occur through electrostatic at-
traction (16). Also, Bisio et al. (17) report
electrostatic interaction of cationic surfactant
with a negatively charged hydrophobic mem-
brane near and above the CMC. It is to be
noted that coal contains, in addition to surface
functional groups, some mineral matter which
imparts a certain degree of charged groups to
coal. However, the low-ash coal used in this
study supports the contention that the ad-
sorption is not augmented by electrostatic in-
teractions between the oppositely charged
species.
Effect of pH on Adsorption
The dependence on pH of the adsorption
of Ey and EyS homologs onto coal at a con-
0
o o o
m ,,
"." "- ; L ~
~ ~ ~ A .
~a
O o o 0
COAL/4XIO-4kmol/m3 SURFACTANT
2X10-3 kmol/m3 NaCl, T= 25 C
i i i i
6 8 i0 12 14
pH
 S U R F A C T A N T A D S O R P T I O N ON COAL 433

stant initial surfactant concentration is illus- Mechanism of Surfactant Adsorption

trated in Fig. 4. While the adsorption remained
constant in the acidic and neutral pH regions,
it showed a gradual decrease in the alkaline
region above approximately pH 9. Insensitiv-
ity of adsorption to pH has been reported for
coal/o-cresol, terpineol, MIBC (6) and also
for coal/dextrin (7) and coal/nonionics sys-
tems (9). This insensitivity of adsorption to
pH was utilized by performing the experiments
at the natural pH (6.8-9.0).
Coal is known to acquire gradual hydro-
philicity above about pH 6 and complete hy-
drophilicity above pH 10 due to the formation
either of surface functional groups (8) or of
hydroxy complexes of multivalent ions on coal
surfaces (18). Insensitivity of adsorption to pH
over a wide range reveals that adsorption oc-
curs predominantly through hydrophobic in-
teractions.
on Coal
The adsorption of ethoxylated sulfonate and
nonionic homologs onto coal is presented in
Fig. 5, where adsorption density is plotted vs
the equilibrium concentration. Langmuir-type
isotherms with the plateau region occurring at
or below CMC were generally obtained. The
CMC values indicated by arrows were ob-
tained using the actual Supernatants.
Nonionic surfactants are known to adsorb
physically on both polar and nonpolar sub-
strates (4, 5, 15, 17, 19-26). Adsorption of
nonionic surfactants on hydrophobic solids
such as coal usually undergoes three or four
stages depending on the nature of adsorbent
and adsorbate. The nonpolar portion of the
molecule, in the first stage, adsorbs on coal via
van der Waals interactions and displaces the

3.0

2.5
CMC o o EIoS
0 u 0 0

~S" 2.0
0E13

i.5

1.0

COAL/SURFACTANT

0,5 2X10" 3 kmol/m 3 NaCi

T = 25 C , pH= 6 . 8 - 9 . 0 ( N a t u r a l )

i i I i i i L
4 8 12 16 20 24 28 32

EQUILIBRIUM CONCENTRATION(CX 105), kmol/m 3

FIG. 5. Adsorption of nonionics and ethoxylated sulfonates on coal.

Journal of Colloid and Interface Science, Vol. 129, No. 2. May 1989
434
weakly adsorbed water molecules from the
surface. In the second stage, the surface which
is almost free of water molecules achieves a
monolayer coverage. The third stage is dom-
inated by lateral interactions of the surfactant
molecules which lead to only a marginal in-
crease in adsorption. Formation of hemimi-
celles on the surface beyond the CMC (24) or
existence of a planar monolayer has been pro-
posed to account for the observations regard-
ing the fourth stage (2). Data from hydrody-
namic layer thickness measurements on poly-
carbonate membrane indicate that nonionics
adsorb horizontally below the CMC, become
vertical near the CMC, and form a bilayer
above the CMC (17). Electrokinetic measure-
ments also confirm the above inference (27).
As shown in Fig. 5, the saturation adsorp-
tion values decreased with increases in the EO
number. Table I presents the calculated cross-
sectional areas of the adsorbate molecules for
each EO number. The marked increase in cal-
culated areas per adsorbate molecule, ranging
from 719 to 1941 A2, suggests that the EO
chain also extends in a fiat configuration along
with the alkyl-aryl hydrophobe. If adsorption
occurred only through vertical orientation of
the alkyl-aryl moiety, the cross-sectional areas
would have been independent of the EO num-
ber. The cross-sectional areas for the n-alkyl
chain (C4H9), benzene ring, EO chain (El0),
and sulfonate group are 26, 25, 145, and 30
A2, respectively. The large values for the cal-
culated areas indicate that both nonionics and
ethoxylated sulfonates are indeed adsorbing
through their alkyl-aryl hydrophobes' lying
fiat on the coal surface. The EO chain is either
weakly adsorbed or free and should be pro-
jected away from the interface with an angle
dictated by the ratio of adsorption and hydra-
tion forces. The large cross-sectional areas
suggest that the EO chain has a low angle of
deflection.
The adsorption of nonionic surfactants on
coal can be described in terms of a Langmuir-
type equation although two of the conditions
are not met: (i) there should be no adsorbate-
solvent interactions; (ii) the adsorbate and
Journal of Colloid and Interface Science, Vot. 129, No. 2, May 1989
M.S. CELIK
solvent molecules should be of the same size.
However, it has been shown that these two
conditions are mutually compensating terms,
resulting in a good Langmuir fit (28). The ad-
sorption isotherms in Fig. 5 were found to ap-
proximately obey a Langmuir-type expression,
Y CK
O . . . . [1]
Fm 1 + CK '
where O is the surface coverage, I'm is the
maximum amount adsorbed, C is the equilib-
rium concentration of the adsorbate in the
bulk, and P is the amount adsorbed at con-
centration C. The equilibrium constant K is
a measure of the partitioning of the surfactant
and water between the surface and bulk so-
lution and is related to the apparent adsorption
free energy (AGads) as
AGads = - R T In K, [2]
where R and T are the gas constant and ab-
solute temperature, respectively. Langmuir
plots of 1/ I' vs 1/ C yielded a straight line with
a slope equal to 1am and intercept at K. The
adsorption free energies calculated using Eq.
[2] are presented in Table I as a function of
the EO number for both Ey and EyS homologs.
As the molecule is lying flat on the surface,
the adsorption energy should increase by a
certain increment for each additional CH2 or
EO group. The magnitude of adsorption free
energy varies between 6.66 and 7.17 kcal/mole
for EyS homologs and between 6.72 and 7.09
kcal/mole for Ey homologs. Since both series
of surfactants yield approximately the same
magnitude of adsorption free energy, it sug-
gests that the adsorption involves hydrophobic
bonding only. The free energies of adsorption
of terpineol, cresol, dextrin, and phenol on
coal have been reported as -9.7, -8.2, -8.0,
and -5.5 kcal/mole, respectively (6, 29). The
standard decrease in the free energy of ad-
sorption per EO group was found to be ap-
proximately 70 cal/mole as shown in Fig. 6.
The value of 102 T- 60 cal/mole obtained by
Klimenko et al. ( 3 0 ) for the activated carbon/
nonionics system is in agreement with the
above data.
 S U R F A C T A N T A D S O R P T I O N O N COAL
-7.2
-7.1
-7.(
?.
%o
-6.~
-6.
-6.d 8 I0
FIG. 6. Effect of EO number on adsorption free energy for coal/surfactant system.
Kronberg et al. (3 I) have shown that with
nonpolar adsorbents, the adsorption energy is
close to the micellization energy. As most
nonpolar adsorbents show similar adsorption
free energies, the solution properties of the
surfactant should be a driving force for ad-
sorption. This can be determined by calculat-
ing the free energies of micellization for the
surfactant using
o CMC, the ethoxylated sulfonates showed a
AGmic = R T In XcMc.
The calculated free energies of micellization
given in Table I demonstrate that about 70 to
80% of the adsorption free energy is due to
nonspecific factors such as orientation of the
surfactant molecules at the coal surface. This
orientation of the surfactant molecule through
contact of its hydrophobic moiety with the
surface and projection of the hydrophilic part
toward the solution necessitates replacement
ofwater-hydrophobic contacts by surfactant-
surfactant contacts between the hydrophobic
portions of the surfactant (31). This effect is
influenced only by the nature of the surfactant.
In the case of nonionics and ethoxylated sul-
fonates about 20 to 30% of the adsorption free
435
EyS
Ey
1 14 16 18 20
EO NUMBER
energy is due to the replacement of surface-
water contacts by surface-hydrophobic moiety
contacts; this effect is dependent only on the
nature of the adsorbent (32).
The zeta potential data corresponding to the
adsorption isotherms given in Fig. 7 generally
followed a particular trend for different EO
numbers. While the nonionics exhibited a
sharper decrease in zeta potentials up to the
[3]
marginal decrease below the CMC. Both sys-
tems yielded almost constant potentials above
approximately the CMC. Since ethoxylated
sulfonates have negative sulfonate groups
projecting toward the solution, their zeta po-
tentials are more negative than those of the
nonionics. Also, the zeta potentials become
slightly more negative with increases in the
EO number for both series due to the mag-
nitude of adsorption being higher with the
lower EO numbers.
Dependence of Adsorption on Temperature
The effect of temperature on the adsorption
of nonionic surfactant (El 5) and ethoxylated
Journal of Colloid and Interface Science, VoI. 129, No, 2, May 1989
436 M.S. CELIK

-40
~ ~ o o 9 O E18S
o ~ EI5S
EIoS
-30

-20

ao ~-o E18
-10 COAL/4XIO
-4 k m o ~ E15
2X10-3kmol/m3 NaCl, T=25C E13

.0 I I
10-5 10-4 10-3 10-2
INITIALSURFACTANTCONCENTRATO
I N,kmol/m3
FIG. 7. Zeta potential of coal vs initial surfactant concentration for various surfactants.

sulfonate (E~5S) is illustrated in Fig. 8 at three factant molecule becomes more hydrophobic
levels of temperature. The adsorption process with increased temperature due to gradual
can again be described by the Langmuir equa- dissolvafion of the EO chain which dominates
tion. However, the adsorption exhibited dras- the properties of the surfactant molecule more
tic changes with increased temperature, par- than the polar sulfonate head. Therefore, the
ticularly for the nonionic surfactant. Such re- increase obtained in saturation adsorption
sults have also been reported in the literature values with ethoxylated sulfonates showed a
(2, 9, 25). Increasing the temperature gener- lower temperature dependence than that ob-
ally reduces the solubility with a concomitant tained with the nonionics.
increase in the surface activity of a nonionic The temperature dependence of adsorption
surfactant. Surfactant-solvent interactions can be utilized to calculate the isoteric heat of
with nonionics are highly temperature-sensi- adsorption for the interaction of the nonionic
tive. Surfactant molecules acquire increased surfactant with the coal surface using the
hydrophobicity upon gradual dissolvation of Clausius-Clapeyron equation in the form
the EO chain (32). This results not only in
din K AH
more compact molecular structure but also in
d(I/T) R ' [4]
enhanced surface activity accompanying
higher saturation adsorption values. The data where K is the equilibrium constant obtained
on the adsorption of nonionic surfactant given from the Langmulr plots and M-/is the isoteric
in Fig. 8 clearly illustrate the sensitivity ofsur- heat of adsorption. The slope of In K vs 1/ T
factant to temperature. plots given in Fig. 9 can be used to calculate
Unlike nonionics, anionic surfactants are AH for El 5and E15S. The thermodynamic data
less affected by temperature. Increasing the tabulated in Table I yielded isoteric heats of
temperature increases the solubility and hence -0.90 and -0.79 kcal/mole for E15 and E~sS,
the CMC with a concomitant decrease in the respectively. The heats of adsorption are ap-
surface activity of an anionic surfactant. But parently small and decrease with the addition
in the case of ethoxylated sulfonate, the sur- of the sulfonate group. It should be noted that
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
 SURFACTANT ADSORPTION ON COAL 437

COAL/SURFACTANT
2XlO-3kmol/m 3 NaCI

71- zx
c~lE

E15 75 C
E15S 75 C
0 E15 50 C
o 50 C
E15S
0 E15 25 C
EIbS 25 C

3F& / ~ u

0 0

Q
0 4 8 12 16 20 24 28 32
EQUILIBRIUM CONCENTRATION(CXI05), kmol/m3

F I G . 8. Effect o f t e m p e r a t u r e on adsorption ofdifferent surfactants o n t o coal.

the use of the Clausius-Clapeyron equation to Effect of Ionic Strength

obtain heats of adsorption from adsorption
isotherms has been a subject of criticism (22-
23) because the interfacial excess inherent in
Eq. [4] is assumed to be independent of tem-
perature. However, Haung et al. (29) found
good agreement between the experimentally
measured calorimetric data and the isoteric
heats of adsorption obtained by means of the
Clausius-Clapeyron equation. The small iso-
teric heats of adsorption values suggest that
these surfactants adsorb on coal primarily via
van der Waals and entropy-driven hydropho-
bic binding.
Results for the adsorption of E15 and E15S
onto coal at two different ionic strengths are
presented in Fig. 10. The changes in ionic
strength can generally affect surfactant ad-
sorption due to (i) compression of the elec-
trical double layer around the coal surface, (ii)
the increase in the effective concentration of
surfactant around the coal surface owing to
the salting-out effect, (iii) lowering of the cloud
point of the nonionic surfactant, and (iv) en-
hanced micellization and consequent reduc-
tion in CMC.
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
438
11.8
11.6
11.4
11.2
I i .0
o
10.8
10.6
2.8
FIG. 9. Plots to determine isoteric heats of adsorption for coal/surfactant system.
The increase in adsorption observed in the
case of nonionic surfactant can be attributed
to the mechanisms listed above except (i). On
the other hand, lateral interactions between
the sulfonate heads of the ethoxylated sulfo-
nate oppose adsorption and miceUization,
whereas salting-out and cloud point lowering
enhance adsorption. It is the net effect of these
two opposing forces that determines the mag-
nitude of adsorption. In the present case, the
net effect seems to be marginal. Therefore, the
effect of ionic strength on adsorption is more
pronounced with the nonionic surfactant.
CONCLUSIONS
1. While the nonionic surfactants shifted
the iep of the coal from 5 to 7.2, the coal par-
ticles in the presence of ethoxylated sulfonates
exhibited constant zeta potentials in the entire
pH range tested. The iep shift observed with
the nonionics is attributed to the displacement
of water molecules by the alkyl chain followed
by a decrease in dipolar interactions.
Journal of Colloid and lnterface Science, Vol. 129, No. 2, May 1989
M.S. CELIK
o
2 9 3 0 3.1 3.2 3.3 3.4
I0-3/T
2. The adsorption of nonionic surfactants
and ethoxylated sulfonates on the coal follows
the Langmuir-type isotherm. Increasing the
EO number reduces the surfactant adsorption
on the coal. The homologs of both surfactants
adsorb primarily via the alkyl-aryl hydro-
phobe's lying flat on the coal surface. The EO
chain and/or sulfonate group is projected to-
ward the aqueous phase. Interestingly, the ad-
sorption of ethoxylated sulfonate is not aug-
mented by the presence of the sulfonate group.
This reveals the negligible effect of electrostatic
interactions between the oppositely charged
species and low-ash coal.
3. The free energy of adsorption varied be-
tween 6.66 and 7.17 kcal/mole for the ethox-
ylated sulfonates and between 6.72 and 7.09
kcal/mole for the nonionic surfactants. The
standard decrease in the free energy of ad-
sorption is found to be approximately 70 cal/
mole per EO group. While 70 to 80% of the
adsorption free energy is due to orientation of
surfactant molecules at the coal surface, 20 to
30% of it accounts for the replacement of sur-
 SURFACTANT ADSORPTION ON COAL 439

12

10

n
~" 0 (-;'

8
o E15 , 2X10 - I kmol/m 3 NaCI
o El5 , 2X10 -3 kmol/m 3 NaCI
x
E15 S , 2XIO - I kmol/m 3 NaCI
6
E15 S , 2X10 -3 kmol/m 3 NaCI

4
cz,
o COAL/SURFACTANT
T= 75 C
2

0 O 4 8, 112 ~6 20, ,
24 2'8 ' 32
EQUILIBRIUM CONCENTRATION(CXIO 5) , kmol/m 3

FIG. 10. Effect of ionic strength on surfactant adsorption onto coal.

face-water contacts by surface-hydrophobic
m o i e t y contacts.
4. T h e isoteric h e a t s o f a d s o r p t i o n calcu-
lated b y m e a n s o f t h e C l a u s i u s - C l a p e y r o n
e q u a t i o n are s m a l l ( - 0 . 7 9 a n d - 0 . 9 0 k c a l /
m o l e for t h e e t h o x y l a t e d s u l f o n a t e a n d n o n -
ionic surfactant, respectively), indicating that
the a d s o r p t i o n is m a i n l y g o v e r n e d b y e n t r o p y -
driven hydrophobic bonding.
ACKNOWLEDGMENTS
The author is grateful to Dr. R.-H. Yoon for providing
the coal sample and to the Hoechst Chemical Co. for sup-
plying the surfaetant samples.
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